CN110180404A - A kind of novel double-layer hollow-fibre membrane and its preparation method and application for membrane distillation - Google Patents
A kind of novel double-layer hollow-fibre membrane and its preparation method and application for membrane distillation Download PDFInfo
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B01D69/08—Hollow fibre membranes
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- B01D71/34—Polyvinylidene fluoride
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The novel double-layer hollow-fibre membrane and its preparation method and application that the invention discloses a kind of for membrane distillation, the double-layer hollow fiber film is using hydrophilic layer as internal layer, hydrophobic layer is outer layer, it include PVDF in the casting solution of the internal layer, include in the casting solution of outer layer P (VDF-co-HFP), preparation method are as follows: spray core liquid, internal layer casting solution, outer layer casting solution from three hole spinning heads, then in turn through the first outer coagulation bath, the second outer coagulation bath phase transformation molding, film wire is obtained by impregnating, being freeze-dried up to double-layer hollow fiber film；The first outer coagulation bath is alcohol water mixed solution, and the second outer coagulation bath is water, and the present invention is simple to operation, and material filming is good, and prepared hollow-fibre membrane film wire structure is uniform, and fenestra is orderly aligned, and preferable flux can be obtained during membrane distillation.
Description
Technical field
The invention belongs to doughnut film preparation and application fields, and in particular in a kind of novel double-layer for membrane distillation
Empty fiber membrane and its preparation method and application
Technical background
It is well known that shortage of fresh water has become a big problem of society, and sea water desalination is the way for solving the problems, such as this
One of diameter, currently, obtaining the main method of fresh water by seawater or bitter has: evaporation, electroosmose process, hyperfiltration
And multistage distillation method etc., the film distillation technology that the way of distillation that fast development is got up in recent years is combined with embrane method is in sea water desalination
Aspect is continuously available application, to solve the problems, such as that shortage of fresh water provides a kind of new way.
Membrane distillation (MD) is a kind of emerging Physical Separation Technology, is constantly subjected to the pass of researcher in the past few decades
Note.Membrane distillation is using hydrophobic microporous barrier as medium, and film two sides aqueous solution not can enter fenestra, only from thermosol
The water vapour of liquid evaporation enters cold side from hot side by fenestra under the driving of film two sides water vapor pressure difference, and cold in cold side
It is solidifying, to achieve the purpose that separate water.Membrane distillation process is the process that gaseous state is spread in fenestra, and mass transfer velocity is fast, unit film surface
Product flux is big, meanwhile, it is carried out under lower than solution boiling point and normal pressure, can use the waste heat of solution itself or the waste heat of factory
Etc. low energy position heat source, reduce cost, it has very high salt rejection rate and cocnentration factor, and has that equipment is simple, operation is easy, film
Long service life, low power consumption and other advantages, therefore, film distillation technology has certain competitiveness in many Seawater Desalination Projects, and this is
A kind of separation process of thermal drivers, wherein microporous barrier is as physical support, by hot solution from the cold house comprising liquid or gas
It separates.Due to process be it is non-isothermal, steam molecule moves to low-pressure membrane by fenestra from high-pressure membrane side (i.e. feed side)
Side (i.e. per-meate side).
Membrane material for membrane distillation should meet hydrophobicity and porosity two requirements, to guarantee that water does not penetrate into micropore
Flux interior and with higher.In addition, enough mechanical strengths, good thermal stability, chemical stability and low thermally conductive system
Number is also necessary to MD membrane material.In recent years, the research and development of MD membrane material focus primarily upon following 3 kinds of membrane materials: poly-
Tetrafluoroethene (PTFE), Kynoar (PVDF) and polypropylene (PP), their hydrophobic performance are all preferable.Above several thin
In aqueous polymer, since PVDF has excellent chemical resistance and heat resistance, and it can be dissolved in there are commonly solvent,
Therefore, it is received more and more attention in various membrane separation process.
In addition in recent years, the concept of novel MD hydrophobic/hydrophilic character composite membrane is used.Based on the object to membrane flux process
Reason understands, it is determined that higher membrane flux requirement.Therefore, the hydrophilic embrane method of Bao Shushui/thickness by exploitation and experiments have shown that.With hydrophily
Mechanical support of the internal layer as brittleness outer layer, thin outer layer are that target generates high vapor flux, have developed hydrophobic/hydrophilic character bilayer
Hollow-fibre membrane.The presence of hydrophilic film greatly reduces between evaporation side and condensation side compared with the hydrophobic membrane of same thickness
Resistance to mass tranfer.On the other hand, since hydrophilic sub-layer is thicker, temperature polarization effect is reduced.
However since the hydrophobic/hydrophilic performance of ectonexine is inconsistent, high molecular polymerization used in used ectonexine
Object is different, during the spinning process it is possible that lamination, ectonexine boundary cannot bond well.
Summary of the invention
In order to solve the deficiencies in the prior art, the first purpose of this invention is to provide a kind of for the novel of membrane distillation
Double-layer hollow fiber film, the double-layer hollow fiber film have excellent mechanical performance and hydrophobic performance, membrane flux big.
The second object of the present invention is the provision of using novel double-layer hollow-fibre membrane made from the preparation method
Preparation method.
The third object of the present invention is to provide the novel double-layer hollow-fibre membrane described in one kind for membrane distillation in water
Application in processing.
A kind of novel double-layer hollow-fibre membrane for membrane distillation of the present invention, the double-layer hollow fiber film are with hydrophilic layer
Internal layer, hydrophobic layer are outer layer, include in the casting solution of the internal layer Kynoar (PVDF), include P in the casting solution of outer layer
(VDF-co-HFP)。
Preferably, the internal layer with a thickness of 102~335 μm, the outer layer with a thickness of 27~83 μm.
Using double-layer hollow fiber film as composite hydrophobic/hydrophilic film in the present invention, therefore it is during the preparation process for interior
Layer with the selection of high molecular polymer in outer layer be it is of crucial importance, Kynoar (PVDF) is with good chemical stability
It is a kind of common membrane material with thermal stability, the present invention is easily sent out in duplicature preparation process as internal layer hydrophilic layer
Raw two layers of lamination, inventor has found through a large number of experiments, using Kynoar-hexafluoropropylene copolymer P (VDF-
Co-HFP it) can effectively prevent being layered, this is because P (VDF-co-HFP) and PVDF composition is close, there is similar intermiscibility, simultaneously
Compared with Kynoar (PVDF) homopolymer, P (VDF-co-HFP) is due to mixing master for the Amorphous Phase of hexafluoropropene (HFP)
It wants in component vinylidene (VDF) block, crystallinity is lower, and free volume is larger.Due to the presence of hexafluoropropene (HFP) group, P
(VDF-co-HFP) fluorine content is higher than Kynoar (PVDF), and it is stronger that this has P (VDF-co-HFP) than PVDF
Hydrophobicity.
A kind of preparation method of the novel double-layer hollow-fibre membrane for membrane distillation of the present invention, by core liquid, internal layer casting solution,
Outer layer casting solution is sprayed from three hole spinning heads, is formed, is obtained then in turn through the first outer coagulation bath, the second outer coagulation bath phase transformation
Film wire is by impregnating, being freeze-dried up to double-layer hollow fiber film；
The internal layer casting solution by 5-15wt% PVDF, 0.5-8wt% additive A and 75-90wt% solvent C group
At；
The outer layer casting solution is by the P (VDF-co-HFP) of 5-15wt%, the additive B and 75-85wt% of 5-12wt%
Solvent D composition；
The first outer coagulation bath is alcohol water mixed solution N, and the second outer coagulation bath is water.
In the present invention, by core liquid, internal layer casting solution, outer layer casting solution respectively from the inner hole of three coaxial hole spinning heads,
Interstitial hole and exit orifice are ejected through the phase transformation into the second outer coagulation bath solution of the first outer coagulation bath together and form.As can be seen that this
Invention passes twice through outer coagulation bath phase transformation molding using double gel bath methods；First outer coagulation bath is alcohol water mixed solution,
Second outer coagulation bath is water, and inventor has found to use casting solution and thin film-forming method of the invention, by specific in the present invention
Double coagulation baths, can be made that pattern is good, hydrophobic performance is good, the hollow-fibre membrane with good mechanical strength.
Inventor regulates and controls the content of PVDF in casting solution and P (VDF-co-HFP) in suitable range, on the one hand,
Selected PVDF and P (VDF-co-HFP) as high molecular polymer in inside and outside casting solution in the case where, need to cooperate PVDF and P
(VDF-co-HFP) content just can ensure that during the spinning process the phenomenon that layering do not occur, and another aspect too high levels are low right
Thickness, hole can also have an impact, and the film as spinning comes out is blocked up, and film can become very fine and close, and porosity is obviously reduced, and film leads to
Amount is also corresponding lower.
Preferably, mass percentage of the PVDF in internal layer casting solution is 10-13%.
Preferably, mass percentage of the P (VDF-co-HFP) in outer layer casting solution is 13-15%.As
It is preferred that the additive A is selected from least one of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA).
Preferably, the additive B is selected from least one of ethylene glycol (EG), glycerine.
In the present invention, it is reacted by the way that additive A in internal layer casting solution, is added with PVDF, on the one hand obtains PVDF excellent
Different hydrophily, while there is big porosity, so as to make to be easier to as hydrophilic inner layer to be flooded profit.
By the way that additive B is added in outer layer casting solution, for improving the pore structure of outer layer.
Preferably, the solvent C is in 1-Methyl-2-Pyrrolidone, 2- methylformamide, 2- methylacetamide
It is at least one.
Preferably, the solvent D in 1-Methyl-2-Pyrrolidone, acetone, 2- methylacetamide at least one
Kind.
Preferably, the molecular weight of the PVDF is 30~700,000, further preferably 68-70 ten thousand.
Preferably, the PVDF is PVDF6020.Inventors have found that the molecular weight for using Su Wei company to produce is 68-
700000 PVDF6020 cooperates three holes one spinning method of the present invention, can further promote doughnut obtained
Performance, for example, further promoting its flux and rejection.
Preferably, the molecular weight of the P (VDF-co-HFP) is 30~700,000.Inventors have found that using Austria, Sigma
The P (VDF-co-HFP) of Delhi surprise company production, is able to ascend the hydrophobic performance of hollow-fibre membrane.
In the present invention, alcohol water mixed solution N is the mixed solution of cell alcohol and/or polyalcohol and water, for example, described
Alcohol solution can be the mixed liquor of at least one of methanol, ethyl alcohol, glycerine and water.
Further preferably, the alcohol water mixed solution N is the mixed solution of ethyl alcohol and water.Inventor's discovery is mixed when alcohol water
The mixed solution that solution N is ethyl alcohol and water is closed, compared to similar alcohol solution (such as isopropanol water solution), what is obtained is hollow
The performance of tunica fibrosa is more excellent, for example, being obviously improved the flux of hollow-fibre membrane, improves its pattern, mechanical strength.
As further preferably, in the alcohol water mixed solution N, the mass fraction of ethyl alcohol is 10~60wt%, excellent
It is selected as 10~20wt%.
Preferably, the core liquid is selected from the mixed of alcohol water mixed solution M or N-Methyl pyrrolidone (NMP) and ethyl alcohol and water
Close solution.
Further preferred, the core liquid is the mixed solution of N-Methyl pyrrolidone (NMP) and ethyl alcohol and water.
Inventor is found through experiments that, when the mixed solution that core liquid is N-Methyl pyrrolidone (NMP) and ethyl alcohol and water, and
When the first outer lime set is the mixed solution of ethyl alcohol and water, the performance of gained hollow-fibre membrane is best.
Still more preferably, when core liquid is the mixed solution of N-Methyl pyrrolidone (NMP) and ethyl alcohol and water, ethyl alcohol
Mass fraction is 5~15wt%, and the mass fraction of N-Methyl pyrrolidone (NMP) is 5~15wt%, by core liquid ethyl alcohol,
NMP content controls in the preferred range, facilitates the hydrophobicity for further improving hollow-fibre membrane obtained, further mentions
Rise the performance of film.
Preferably, film wire passes through the air gap height of 5~20cm, further preferably 10cm before entering coagulation bath.
The distance of the output end of three hole spinning heads and the second outer lime set liquid level is air gap height；From the defeated of three hole spinning heads
Outlet output the air of casting solution, core liquid through the air gap height volatilization the effects of, cooperate the casting solution, core liquid,
The component of first outer lime set can help to the intensity for further promoting doughnut, improve its pattern.
Preferably, the speed that internal layer casting solution sprays spinning head is 4-5mL/min, outer layer casting solution sprays spinning head
Speed is 1-2mL/min, and the speed that core liquid sprays spinning head is 1-4mL/min, preferably 1-3mL/min.
In the present invention, the high-performance hollow tunica fibrosa that obtain not stratified, hydrophilic thick-layer, hydrophobic thin film, in spinning
Be also to the control of the spouting velocity of internal layer casting solution, outer layer casting solution etc. in journey it is vital, only pass through three kinds of film liquids
Spouting velocity mutually cooperateed with the component content in inside and outside casting solution, the present invention could be obtained for membrane distillation with hydrophobic/close
Aqueous double-layer hollow fiber film.
Preferably, the temperature of internal layer casting solution, outer layer casting solution, core liquid, the first outer lime set is 10~50 DEG C.
Further preferably, internal layer casting solution, outer layer casting solution temperature be 30 DEG C, the temperature of core liquid and the first outer lime set is equal
It is 25 DEG C.
In the present invention, casting solution, core liquid are sprayed into the first outer lime set bath, and the film wire come out after bath solidifying outside second is put
It is impregnated 2~4 days in deionized water, subsequent chilled machine freeze-drying process, preferred sublimation drying is 2-6h.
A kind of application of the novel double-layer hollow-fibre membrane for membrane distillation of the present invention, the double-layer hollow fiber film is answered
It is handled for sea water desalination.
Beneficial effect
The present invention selects have the poly- inclined of similar units structure using double-layer hollow fiber film as composite hydrophobic/hydrophilic film
Vinyl fluoride (PVDF), Kynoar-hexafluoropropene P (VDF-co-HFP) are respectively as the high molecular polymerization for preparing ectonexine
Object can effectively prevent inside and outside by combining the component content of high molecular polymer and the flow proportional of inside and outside casting solution
There is a phenomenon where be layered during the preparation process for film.
Simultaneously it is a discovery of the invention that using double gel bath methods, and the effectively outer lime set bath of selection first, the second outer lime set
Bath, the composition of core liquid and content, can make the pattern of ectonexine film more excellent, obtain excellent membrane flux.
The present invention is simple to operation, and material filming is good, and prepared hollow-fibre membrane film wire structure is uniform, fenestra arrangement
Orderly, preferable flux can be obtained during membrane distillation, the use of polymer P (VDF-co-HFP) improves the hydrophobicity of film,
Rejection is realizing that there are great potentials in its industrial applications up to 99% or more.
Detailed description of the invention
Fig. 1 is hollow-fibre membrane section made from embodiment 1 and inside and outside SEM figure；Wherein, a-1, a-2 are sectional view；B is
Inner surface SEM figure, c are outer surface SEM figure；
Fig. 2 is hollow-fibre membrane section made from embodiment 2 and inside and outside SEM figure；Wherein, a-1, a-2 are sectional view；B is
Inner surface SEM figure, c are outer surface SEM figure；
Fig. 3 is hollow-fibre membrane section made from comparative example 1 and inside and outside SEM figure；Wherein, a-1, a-2 are sectional view；B is
Inner surface SEM figure, c are outer surface SEM figure；
Obviously, in terms of the electron microscopic picture of spinning three times, inner surface (in b-) obviously may be used than outer (outside c-) porous surface
To find out that inner surface aperture is greater than outer surface aperture, from section (a), the thickness of hydrophilic inner layer is obviously thicker than hydrophobic outer layer.Its
In, doughnut film inner layer average thickness made from embodiment 1 is 331 μm as can be seen from Figure 1, and outer layer average thickness is 31 μ
m；Doughnut film inner layer average thickness made from embodiment 2 is 112 μm as can be seen from Figure 2, and outer layer average thickness is 73 μm；
Doughnut film inner layer average thickness made from embodiment 3 is 194 μm as can be seen from Figure 3, and outer layer average thickness is 108 μm.
I.e. prepared is hydrophilic thick-layer, hydrophobic thin film.And comparative example 1 is excessive so that outer layer mistake due to outer layer casting solution concentration
Thickness causes membrane flux small, while can be seen that and the phenomenon that ectonexine layering also occur.
Specific embodiment
Wherein: used is the PVDF6020 for being purchased from Su Wei company, and molecular weight is 68-70 ten thousand.
P (VDF-CO-HFP) used is purchased from Sigma-Aldrich, and molecular weight is 30-70 ten thousand.
Spinning head is that three hole spinning heads are purchased from Ningbo Si Binna company.
Embodiment 1
1. the preparation of ectonexine casting solution, core liquid and outer coagulation bath
Internal layer casting solution uses Kynoar (PVDF6020), additives polyvinyl alcohol (PVA), Solvents N-methyl pyrroles
Alkanone (NMP) three kinds of substances in percentage by weight 10wt%, 0.5wt%, 89.5wt% are uniformly mixed at 60 DEG C；Outer casting solution
Using Kynoar-hexafluoropropene (P (VDF-co-HFP)), additive ethylene glycol (EG), solvent n,N-dimethylacetamide
(DMAc) three kinds of substances in percentage by weight 15wt%, 5wt%, 80wt% are uniformly mixed at 60 DEG C；The group of core liquid becomes second
The mixture of alcohol and water, weight percent are prepared by 50/50wt%；The group of first outer coagulation bath becomes the mixing of ethyl alcohol and water
Object, weight percent are prepared by 10/90wt%, and the second outer coagulation bath is water.
2. the spinning of hollow-fibre membrane
By core liquid, internal layer casting solution, outer layer casting solution respectively from inner hole, interstitial hole and the exit orifice of three coaxial hole spinning heads
It sprays together, the film wire of formation successively passes through the first outer gel after the air gap height of 10cm, with the wire winding speed of 5m/min
Bath phase transformation into the second outer coagulation bath solution forms, and collects after forming after phase transformation, and internal layer casting film flow velocity is 4.6ml/
Min, outer layer casting film flow velocity are 1.5ml/min, and core flow velocity is 2ml/min；30 DEG C of casting solution temperature, core liquid temperature is 25
DEG C, coagulation bath temperature is 25 DEG C.
3. hollow-fibre membrane post-processes
The film wire of collection is first placed into deionized water and is impregnated 72 hours, remaining polar solvent is removed, then with cold
It is dry to get finished product that lyophilizer carries out pre-freeze.
Manufactured film wire is separated by membrane distillation and is tested, and film average flux is 4.26kgm3h-1, rejection 99.9%.
Embodiment 2
It is compared with embodiment 1, the flow velocity of adjustment casting solution, core liquid and the first outer coagulation bath is specific as follows:
1. the preparation of casting solution, core liquid and outer coagulation bath
Internal layer casting solution uses Kynoar (PVDF6020), additive polyvinylpyrrolidone (PVP), solvent N- first
Base pyrrolidones (NMP) three kinds of substances in percentage by weight 13wt%, 8wt%, 79wt% are uniformly mixed at 60 DEG C；Outer casting film
Liquid uses Kynoar-hexafluoropropene (P (VDF-co-HFP)), additive ethylene glycol (EG), solvent N, N- dimethylacetamide
Amine (DMAc) three kinds of substances in percentage by weight 13wt%, 12wt%, 75wt% are uniformly mixed at 60 DEG C；The group of core liquid becomes
The mixture of N-Methyl pyrrolidone, second alcohol and water, weight percent 5wt%, 10wt%, 85wt%, the first outer coagulation bath
Group become ethyl alcohol and water mixture, weight percent by 20/80wt% prepare, the second outer coagulation bath be water.
2. the spinning of hollow-fibre membrane
By core liquid, internal layer casting solution, outer layer casting solution respectively from inner hole, interstitial hole and the exit orifice of three coaxial hole spinning heads
It sprays together, the film wire of formation successively passes through the first outer gel after the air gap height of 10cm, with the wire winding speed of 5m/min
Bath phase transformation into the second outer coagulation bath solution forms, and collects after phase transformation molding, and internal layer casting film flow velocity is 4.6ml/min,
Outer layer casting film flow velocity is 1.5ml/min, and core flow velocity is 2ml/min；30 DEG C of casting solution temperature, core liquid temperature is 25 DEG C, is coagulated
Glue bath temperature is 25 DEG C.
3. hollow-fibre membrane post-processes
The film wire of collection is first placed into deionized water and is impregnated 72 hours, remaining polar solvent is removed, then with cold
It is dry to get finished product that lyophilizer carries out pre-freeze.
Manufactured film wire is separated by membrane distillation and is tested, and film average flux is 7.12kgm3h-1, rejection 99.9%.
Comparative example 1
1. the preparation of outer layer casting solution, core liquid and outer coagulation bath
Internal layer casting solution uses Kynoar (PVDF6020), additive polyvinylpyrrolidone (PVP), solvent N- first
Base pyrrolidones (NMP) three kinds of substances in percentage by weight 10wt%, 8wt%, 82wt% are uniformly mixed at 60 DEG C；Outer casting film
Liquid uses Kynoar-hexafluoropropene (P (VDF-co-HFP)), additive ethylene glycol (EG), solvent N, N- dimethylacetamide
Amine (DMAc) three kinds of substances in percentage by weight 19wt%, 8wt%, 73wt% are uniformly mixed at 60 DEG C；The group of core liquid becomes
The mixture of N-Methyl pyrrolidone, second alcohol and water, weight percent 15wt%, 10wt%, 75wt%；First outer coagulation bath
It is water with the second outer coagulation bath.
2. the spinning of hollow-fibre membrane
By core liquid, internal layer casting solution, outer layer casting solution respectively from inner hole, interstitial hole and the exit orifice of three coaxial hole spinning heads
It sprays together, the film wire of formation successively passes through the first outer gel after the air gap height of 10cm, with the wire winding speed of 5m/min
Bath phase transformation into the second outer coagulation bath solution forms, and collects after forming after phase transformation, and internal layer casting film flow velocity is 4.6ml/
Min, outer layer casting film flow velocity are 1.5ml/min, and core flow velocity is 2ml/min；30 DEG C of casting solution temperature, core liquid temperature is 25
DEG C, coagulation bath temperature is 25 DEG C.
3. hollow-fibre membrane post-processes
The film wire of collection is first placed into deionized water and is impregnated 72 hours, remaining polar solvent is removed, then with cold
It is dry to get finished product that lyophilizer carries out pre-freeze.
Manufactured film wire is separated by membrane distillation and is tested, and film average flux is 3.18kg.m-2.h-1, rejection
99.9%.
Comparative example 2
Other conditions are same as Example 2, and only outer layer casting film flow velocity is 4ml/min, as a result occur during the spinning process
Lamination.
Comparative example 3
Other conditions are same as Example 2, and it is 6ml/min, internal layer thickness that only internal layer casting solution, which sprays the speed of spinning head,
Blocked up, membrane flux is small.
Claims (10)
1. a kind of novel double-layer hollow-fibre membrane for membrane distillation, it is characterised in that: the double-layer hollow fiber film is with hydrophilic
Layer is internal layer, and hydrophobic layer is outer layer, includes PVDF in the casting solution of the internal layer, includes P (VDF-co- in the casting solution of outer layer
HFP)。
2. a kind of novel double-layer hollow-fibre membrane for membrane distillation according to claim 1, it is characterised in that: in described
Layer with a thickness of 102~335 μm, the outer layer with a thickness of 27~83 μm.
3. preparing a kind of method of the novel double-layer hollow-fibre membrane for membrane distillation as claimed in claim 1 or 2, feature
It is: core liquid, internal layer casting solution, outer layer casting solution is sprayed from three hole spinning heads, then in turn through the first outer coagulation bath,
Two outer coagulation bath phase transformation moldings, obtain film wire by impregnating, being freeze-dried up to double-layer hollow fiber film；
The internal layer casting solution is made of the additive A of PVDF, 0.5-8wt% and the solvent C of 75-90wt% of 5-15wt%；
The outer layer casting solution is molten by the P (VDF-co-HFP) of 5-15wt%, the additive B of 5-12wt% and 75-85wt%'s
Agent D composition；
The first outer coagulation bath is alcohol water mixed solution N, and the second outer coagulation bath is water.
4. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: the additive A is selected from least one of PVP, PVA, the additive B in ethylene glycol, glycerine at least
One kind, the solvent C are selected from least one of 1-Methyl-2-Pyrrolidone, 2- methylformamide, 2- methylacetamide, institute
It states solvent D and is selected from least one of 1-Methyl-2-Pyrrolidone, acetone, 2- methylacetamide.
5. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: the alcohol water mixed solution N is the mixed solution of ethyl alcohol and water, in the alcohol water mixed solution N, the quality point of ethyl alcohol
Number is 10~60wt%.
6. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: the core liquid is selected from the mixed solution of alcohol water mixed solution M or NMP and ethyl alcohol and water, when core liquid is NMP and ethyl alcohol and water
Mixed solution when, the mass fraction of ethyl alcohol is 5~15wt%, and the mass fraction of NMP is 5~15wt%.
7. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: film wire passes through the air gap height of 5~20cm before entering the first outer coagulation bath.
8. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: the speed that internal layer casting solution sprays spinning head is 4-5mL/min, and the speed that outer layer casting solution sprays spinning head is 1-2mL/
Min, the speed that core liquid sprays spinning head is 1-4mL/min.
9. a kind of preparation method of novel double-layer hollow-fibre membrane for membrane distillation according to claim 3, feature
Be: internal layer casting solution, outer layer casting solution, core liquid, the first outer lime set temperature be 10~50 DEG C.
10. a kind of application of novel double-layer hollow-fibre membrane for membrane distillation according to claim 1 or 2, feature
It is: the double-layer hollow fiber film is handled applied to sea water desalination.
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